Resorcinol-formaldehyde-latex adhesive containing triallyl cyanurate with high-ringbound chlorine content

ABSTRACT

A composition comprising an aqueous dispersion of A. 50-95 parts of a resorcinol-formaldehyde-latex adhesive composition, B. 5-50 parts of an aqueous dispersion of 10-70 percent of the reaction product of 1. A COMPOSITION DERIVED BY REACTING A TRIALLYL CYANURATE COMPOSITION HAVING 0.05 TO 3.0 PERCENT RING-BOUND CHLORINE, WITH 6-10 MOLES OR RESORCINOL PER MOLE OF CYANURATE; AND 2. 0.2 TO 0.6 MOLE OF FORMALDEHYDE PER MOLE OF RESORCINOL IN (1) These compositions are useful in bonding rubber to reinforcing fibers. This invention relates to materials and methods for improving the adhesion of nonrubbery materials to rubber. The invention further relates to processes for preparing novel compositions used in the method of this invention. It is known to incorporate shaped structures, such as films, cords and fibrous textile materials, and particularly, polyamide and polyester fibers, into rubber, in order to reinforce the rubber and improve the wearing qualities of the resultant rubber articles. This is particularly important in the case of tires, conveyor belts, transmission belts and, in general, articles which are subjected to severe loads. This method, however, has been far from satisfactory, because the fibrous material during usage, separates from the rubber. The separation usually is accompanied by generation of heat, tears and frequently complete breakdown of the article. Many attempts have been made to improve the adhesion of the fibrous materials to rubber in order to obtain products of improved wearing quality and strength. The method of Canadian Pat No. 625,487 consists of reinforcing rubber with fibrous material of the polymethylene terephthalate type, using a two-coat adhesive system. The first coat consists of triallyl cyanurate which may also contain vinyl chloride. The second coat is a dispersion of a polymer of vinylpyridine and a resorcinolformaldehyde-la-tex composition. The fibrous material is coated with triallyl cyanurate, and the latter polymerized by heating. Although this method has given some improvement in bonding properties between the fibrous material and the rubber, the prolonged heating necessary to polymerize triallylcyanurate is a serious disadvantage. Moreover, this method does not give sufficiently reproducible results. More recently, U.S. Pat. No. 3,318,750 describes a method in which the fibrous material is coated with (1) an aqueous solution of the reaction product of an aldehyde and a composition derived from the reaction of triallyl cyanurate and an excess of a polyhydric phenol and (2) a resorcinol-formaldehyde-latex adhesive composition. The coated material is heated, embedded in vulcanizable rubber and the rubber vulcanized. The adhesive compositions of this patent have undoubtedly resulted in superior bonding of the reinforcing material to the rubber and thus in superior finished articles; however, under the action of heavy loads and the stresses to which many rubber articles, for instance tires, are subjected, these products do not exhibit sufficient strength. The adhesives proposed in U.S. Pat. No. 3,307,966 contain a Polyepoxide and a polyisocyanate and are objectionable because of the toxicity of the polyisocyanate and the problems involved in finding a suitable solvent for application of the adhesive. An object of this invention is to provide novel compositions capable of improving the adhesion between fibrous materials and rubber. Another object is to provide compositions which are economical, suitable for commercial application, and which may be applied to a variety of fibers, and particularly synthetic fibers such as fiber glass, polyester fibers and the like. Still other objects will be apparent from the ensuing description of this invention.

United States Patent Broisman 51 Feb. 22, 1972 [54]RESORCHNOL-FORMALDEHYDE- LATEX ADHESIVE CONTAINING TRIALLYL CYANURATEWITH HIGH- RINGBOUND CHLORINE CONTENT Raymond Broisman, Linden, NJ.

American Cyanamid Company, Stamford, Conn.

Filed: Aug. 8, 1969 Appl. No.: 848,690

inventor:

Assignee:

US. Cl ..260/29.3, 156/110, 156/331, 156/335, 161/198, 161/227, 161/231,161/241, 260/515, 260/54, 260/845, 260/848 1111, (:1 ..C08g 5/10 FieldoiSaarch ..260/29.3, 51.5, 54, 845,846, 260/848; 161/227, 198, 231, 241,257; 156/110,

[56] References Cited UNITED STATES PATENTS 3,304,222 2/ 1967 Wilken..260/29.3

Aitken..

3,424,608 1/ 1969 Marzocchi et al. ..260/29.3 3,476,642 11/1969 Berg etal 3,476,701 11/1969 Aldred et a1. 3,549,481 12/1970 Cesare 1 61/198Primary Examiner-Donald J. Arnold Attorney-James H. Laughlin, in

[57] ABSTRACT These compositions are useful in bonding rubber toreinforcing fibers.

4 Claims, No Drawings RESORCKNOL-FORMALDEHYDE-LATEX ADHESIVE CONTAININGTRIALLYL CYANURATE WITH HIGH- RINGBOUND CHLORINE CONTENT This inventionrelates to materials and methods for improving the adhesion ofnonrubbery materials to rubber. The invention further relates toprocesses for preparing novel compositions used in the method of thisinvention.

It is known to incorporate shaped structures, such as films, cords andfibrous textile materials, and particularly, polyamide and polyesterfibers, into rubber, in order to reinforce the rubber and improve thewearing qualities of the resultant rubber articles. This is particularlyimportant in the case of tires, conveyor belts, transmission belts and,in general, articles which are subjected to severe loads. This method,however, has been far from satisfactory, because the fibrous materialduring usage, separates from the rubber. The separation usually isaccompanied by generation of heat, tears and frequently completebreakdown of the article.

Many attempts have been made to improve the adhesion of the fibrousmaterials to rubber in order to obtain products of improved wearingquality and strength. The method of Canadian Pat No. 625,487 consists ofreinforcing rubber with fibrous material of the polymethyleneterephthalate type, using a two-coat adhesive system. The first coatconsists of triallyl cyanurate which may also contain vinyl chloride.The second coat is a dispersion of a polymer of vinylpyridine and aresorcinol-formaldehyde-la-tex composition. The fibrous material iscoated with triallyl cyanurate, and the latter polymerized by heating.Although this method has given some improvement in bonding propertiesbetween the fibrous material and the rubber, the prolonged heatingnecessary to polymerize triallylcyanurate is a serious disadvantage.Moreover, this method does not give sufficiently reproducible results.

More recently, U.S. Pat. No. 3,318,750 describes a method in which thefibrous material is coated with (1) an aqueous solution of the reactionproduct of an aldehyde and a composition derived from the reaction oftriallyl cyanurate and an excess of a polyhydric phenol and (2) aresorcinol-formaldehyde-latex adhesive composition. The coated materialis heated, embedded in vulcanizable rubber and the rubber vulcanized.The adhesive compositions of this patent have undoubtedly resulted insuperior bonding of the reinforcing material to the rubber and thus insuperior finished articles; however, under the action of heavy loads andthe stresses to which many rubber articles, for instance tires, aresubjected, these products do not exhibit sufficient strength.

The adhesives proposed in U.S. Pat. No. 3,307,966 contain a polyepoxideand a polyisocyanate and are objectionable because of the toxicity ofthe polyisocyanate and the problems involved in finding a suitablesolvent for application of the adhesive.

An object of this invention is to provide novel compositions capable ofimproving the adhesion between fibrous materials and rubber. Anotherobject is to provide compositions which are economical, suitable forcommercial application, and which may be applied to a variety of fibers,and particularly synthetic fibers such as fiber glass, polyester fibersand the like.

Still other objects will be apparent from the ensuing description ofthis invention.

In accordance with one aspect of this invention, it has been found thatthe triallyl cyanunate-resorcinol-formaldehyde reaction product and aresorcinol-formaldehyde-latex adhesive composition give superioradhesion when the triallyl cyanurate contains a compound having chlorineattached to a triazine ring. The proportion of ringbound chlorinecalculated as cyanuric chloride, should be between about 0.05 and 3.05percent based on the weight of triallyl cyanurate. In view of the factthat the ringbound chlorine is reactive and that it may cause sidereactions, including undesirable exothermic reactions, the generalpractice in the art has been to purify the product and to use eitherpure triallyl cyanurate or triallyl cyanurate with low-ringboundchlorine content, in the range of 0.01-0.02 Percent. Thus the findingthat superior adhesion between the fibrous materials and the rubber isachieved with ringbound chlorine up to 3.08, is unexpected andsurprising.

The compositions useful for improving the adhesion between rubber andfibrous materials, according to the present invention, comprisecomponent A a resorcinol-formaldehyde-latex adhesive mixture(hereinafter sometimes referred to as the RFL dip) and component B thereaction product of triallyl cyanurate (sometimes referred tohereinafter as TAC) which contains between 0.05 and 3.0 percent ofringbound chlorine, resorcinol and formaldehyde. The adhesivecompositions to be applied to the fibrous materials comprise 50 to partsof component A and 5 to 50 parts of component B.

The compositions of this invention are applied to the fibrous materialsby any conventional method, such as for instance, dipping, spraying,brushing, or padding. Reaction of components A and B occurs upon drying,and heating at about -250 C. for up to about 2 minutes. In this manner,the adhesive composition is cured and forms a coating upon the fibrousmaterial which constitutes about 2-10 percent by weight of the totalfiber weight. It is preferable to subject the fibrous materials tosufficient tension during the wetting and curing operations to preventshrinkage. Following the formation of the coating on the fibrousmaterial, rubber is applied by conventional techniques.

The compound within component B which contains ringbound chlorine, maybe triazine of the formula (I):

Y-fiJ-(h Y in which Y and Z are individually either chlorine, hydroxy orallyloxy groups. Cyanuric chloride, monochloro-dihydroxy-striazine,dichloro-monohydroxy-s-triazine monochloro-diallyloxy-s-triazine anddichloro-allyloxy-s-triazine are specific compounds within the scope offormula I which can be used to supply the RBC content of component B.

TAC is conveniently prepared by the method described in U.S. Pat. No.2,537,816. The method consists of admixing allyl alcohol in substantialexcess over the theoretical amount of 3 moles per mole of cyanuricchloride with cyanuric chloride in the presence of at least 3 moles ofan alkali metal hydroxide. Alkali metal carbonates or calcium or bariumhydroxide may also be used. By way of example, the reaction is carriedout by dissolving at least 3 molar equivalents of sodium hydroxide, in aleast 3 molar equivalents of allyl alcohol, at about 20-30 C., stirring,and slowly adding one molar equivalent of cyanuric chloride. After thereaction is complete, sodium chloride is filtered off, and the filtercake washed with allyl alcohol. The desired triallyl cyanurate is thenobtained from the combined filtrate and washings by distilling the allylalcohol under vacuo. The crude product may be purified by repeatedlywashing with sodium hydroxide and water.

Triallylcyanurate ordinarily contains no more than a trace of ringboundchlorine, e.g., about 0.01-0.02 percent of RBC, several methods may beused. This it is possible to use less than the required amount of baseor of allyl alcohol, so that an insufficient amount of either reactantis present to complete the replacement of the three chlorine atoms ofcyanuric chloride.

It is also possible to use a less concentrated sodium hydroxidesolution. More specifically when pure TAC is desired, 50 percent sodiumhydroxide, in a slight excess, about 2-3 percent, is dissolved in allylalcohol in a substantial excess, about 50 percent, at 2014 30 C. Thencyanuric chloride is added. The product is purified by repeated sodiumhydroxide and water washing. lf triallyl cyanurate of high-ringboundchlorine content, i.e., having between 0.05 and 3.0 percent is to beprepared, it is possible to use 25-50 percent aqueous sodium hydroxidein less than the stoichiometric amount during the reaction. It has alsobeen found that if the amount of allyl alcohol used is less than 50percent excess, the product contains ringbound chlorine A calculatedamount of this substance may be added to TAC of low-RBC content, i.e.,0.01-0.02 percent ringbound chlorine, to give TAC of the desiredringbound chlorine content.

A rubbery copolymer latex suitable for use in preparing the REL-adhesivecomposition is a vinyl pyridine copolymer latex sold under the trademarkGENTAC" by the General Tire and Rubber Company. This latex is an aqueousdispersion of a terpolymer derived from the copolymerization of 70percent by weight of butadiene, 15 percent of vinylpyridine and 15percent by weight of styrene. The dispersion normally contains about 40percent of elastomer solids. Another suitable copolymer latex isPliolite 2108 which is the trademark of the Goodyear Tire and RubberCompany for the styrene-butadiene rubber latex derived from thecopolymerization of 29 percent by weight of styrene and 71 percent byweight of butadiene. A mixture of Gentac and Pliolite 2108 is apreferred latex for the adhesive compositions of this invention. Otherlatices, such as natural and butyl rubber may also be employed. Theselection of the rubbery latex is determined by the type of rubber stockemployed and it is within the skill of the art to choose the latex whichsuits the rubber stock.

The adhesive properties of the compositions of this invention aredetermined by coating the shaped structures, fibrous materials and thelike with the compositions of this invention, drying and heating to curethe compositions, then embedding the coated material in vulcanizablerubber and finally vulcanizing the rubber. The tension necessary tostrip the fibrous material from the elastomer sheet is then determined.

Although the coating of the fibrous materials with the adhesivecompositions of this invention may be obtained by separately applyingcomponents A and B in either order, in a liquid carrier which may be thesame or different, it is preferable to combine the two components in asingle liquid carrier, and apply the mixture to the fibrous material.According to a preferred embodiment of the invention, components A and Bin water as a liquid carrier, are mixed and the fibrous materials aredipped into the mixture.

The rubber stock is either a natural material or a syntheticstyrene-butadiene rubber. The rubber referred to in the tests iscompounded by mixing the ingredients below on a two-roll rubber mill,sheeting off and protecting one surface with a polyethylene filmPreformed strips of appropriate size are then cut from the sheet ofrubber stock without removing the polyethylene film.

The natural rubber stock has the following composition:

Component Parts by Weight No. l Ribbed Smoked Sheets I Stcaric Acid 2Easy Processing Channel Black l0 Fast Extruding Furnace Black 20 ZincOxide 5 Light Process Oil Octylated Di henylamine Antioxidant SulfurMBTS The synthetic styrene-butadiene rubber has composition:

the following For the purpose of better illustrating the invention, thefollowing examples are described liereinbelow. Parts and percentages areon a weight basis.

EXAMPLE 1 This example shows the preparation of TAC containing no morethan a trace amount (i.e., 0.01 percent) of any compound having chlorinebonded to a triazine ring. The reaction involves a total of 4,000 pounds(68.9 moles) of real allyl alcohol with 2,800 pounds (15.2 moles) ofcyanuric chloride, and 1,984 pounds of real sodium hydroxide as a 50percent aqueous solution (46.6 moles of sodium hydroxide).

The allyl alcohol (51 percent excess) is pumped into a reactor and the50 percent sodium hydroxide solution and cyanuric chloride are addedconcurrently. The temperature is maintained at 2025 C. The excess sodiumhydroxide is neutralized with hydrochloric acid, the excess allylalcohol is stripped off under vacuum and the sodium chloride isdissolved in water which is separated from the crude triallylcyanuratelayer. The crude triallyl cyanurate is washed once with 5 percent sodiumhydroxide and then three times with water to remove reaction impurities.The residual water is then stripped ofi under vacuum, a polymerizationinhibitor is added and the TAC is filtered off and collected. Theproduct has a ringbound chlorine content of 0.01 percent.

EXAMPLE 2 This example illustrates the preparation of TAC containingabout 2.37 percent of ringbound chlorine. The reaction involves a totalof 2,645 pounds (45.5 moles) of allyl alcohol with 2,800 pounds (15.2moles) of cyanuric chloride and 1,865 pounds (46.6 moles) of causticsoda as a 50 percent aqueous solution.

The allyl alcohol (0% excess) is pumped into a reactor and the 50sodiumhydroxide solution and cyanuric chloride are added concurrently. Thetemperature of the reaction is maintained at 20 to 25 C. The excessNaOl-l is neutralized with hydrochloric acid and the salt is dissolvedin water which is then separated from the crude TAC layer. The crude TACis washed once with 5 percent sodium hydroxide and three times withwater to remove reaction impurities. Residual water is then strippedunder vacuum, a polymerization inhibitor is added and the TAC iscollected. The product is a water-white oily liquid having a ring boundchlorine content of 2.37 percent.

EXAMPLE 3 TABLE Relationshi of RBC Content to Percent Excess AllylAlcohol Excess Allyl Alcohol (5) Ring-bound Chlorine EXAMPLE 4 Thisexample illustrates the preparation of TAC with high- RBC content byreducing the amount of sodium hydroxide used in the beginning of theesterification reaction and then adjusting to the desired RBC content byaddition of additional sodium hydroxide at the end of the reaction.

Following the procedure of Example 2. 68.9 moles of allyl alcohol, 15.2moles of cyanuric chloride and 35 moles of sodium hydroxide were chargedinto a reactor in which the temperature was maintained at 20 to 25 C.After about 6 hours, a 50 percent caustic solution containing 1 1.6moles of sodium hydroxide was added in increments.

EXAMPLE This example illustrates the preparation of TAC containing about0.8 percent REC by conducting the esterification in dilute caustic.

The procedure of Example 4 is varied by adjusting the concentration ofthe caustic which is added to the reaction mixture at the commencementof the reaction. Thus, instead of adding 50 percent caustic, the reactoris charged with 25 caustic so that approximately 17.5 moles of sodiumhydroxide is present. At the end of the reaction, the remainder of thesodium hydroxide is then added.

EXAMPLE 6 This example illustrates the preparation of TAC containingringbound chlorine by the addition of at least one compound containingringbound chlorine to TAC.

The product of Example 1 (100 grams) is charged into a vessel and 0.5grams of diallyoxy-monochloro-s-triazine is added. The mixture isstirred, giving a TAC product with a ringbound chlorine content of 0.5percent. Similarly, a TAC product with 2.0 percent of ring-boundchlorine is obtained by the addition of two grams ofdiallyloxy-monochloro-s-triazine to 100 grams of TAC produced as inExample 1 above.

EXAMPLE 7 A resorcinol-formaldehyde-latex adhesive composition(component A) was prepared from the following ingredients:

Parts by Weight Gentac polyvinylpyridine latex of about 41% solids 316.0

Pliolite 2l0l3 styrene-butadiene rubber latex of about 40.7%

solids 77.0

Water 5128 Resorcinol 27.4 Formalin (37% Formaldehyde) 24.2 5% NaOH 42.61,000.0

Components Parts by Weight Resorcinol 17.23

TAC 4.l4

Red Lead 0.04 Formaldehyde (33%) 4.83 Ammonium Hydroxide (28%) 4.83Water 6893 The resorcinol is heated to 180 C. in a one-liter flaskfitted with a mechanical agitator, thermometer and condenser. At 180 C.,with agitation, the TAC is added and the temperature is allowed to riseto 225 C The red lead is added and the mixture kept at 220-225 C. for 3hours. it is cooled to 130 C. and the formaldehyde is added slowly tomaintain the reaction temperature at 130 C. The water and ammoniumhydroxide are mixed and added to the mixture in the flask. The resultantmixture is agitated well, cooled to room temperature and filtered. TheTable below summarizes the samples of TAC used.

RBC Content of TAC Solution No. Amount of ring-bound A clip for tirecord was prepared as follows: Samples of 50 parts by weight of SolutionNo. l or 2 or 3 above were added to parts of the RFL mixture component Aprepared as described hereinabove. The following Table shows thecomposition of each dip and of a control having no component B:

Test samples of polyester tire cord were dipped in the adhesivemixtures, then dried by heating for 2 minutes at 100 C., and heattreated at 250 C. for 2 minutes while subjected to tension, to preventshrinkage.

The strength of the adhesive bond of the treated cords to the carcassstocks was evaluated by a modification of the Single End Strip Adhesiontest, described in U.S.P. at No. 3,307,966. The mold used had multiplecavities approximately lX6 1/4 inch, and had metal strips on twoopposite sides bearing slots so located that four lengths of cord couldbe positioned longitudinally over each cavity. The mold was preheated tothe vulcanization temperature. A strip of cotton duck 1X6 inches wasplaced in the bottom of each cavity, then the preformed carcass stock,protected side up, was placed over the cord, and the protectivepolyethylene film was then stripped off. Four lengths of cord wereplaced over each strip of stock, with each cord in the same strip havingreceived the same treatment. A small strip of Cellophane was insertedbetween the cords and the rubber stock at one end of the structure, sothat a portion of each cord remained free from clamping during the test.The cords were under a deadweight tension of approximately 50 grams percord, to maintain their position. The top plate was placed on the mold,and the latter was then pressed in a platen press. vulcanization wasthen carried out, 40 minutes with the natural rubber and 45 minutes withthe styrene-butadiene stock, both at 138 C. The samples were thenremoved from the press. It was noted that the cords were firmly embeddedin the cured elastomer stock. The cord ends were separated from one endof the strip and the free end of the strip was clamped in the upper jawof an lnstron testing machine, while the freed end of one cord wasclamped in the lower jaw. The tension necessary to strip the singlecords individually from the elastomer strip at a jaw separation speed of2 inches per minute was then determined. The results, reported as thetension necessary to strip the cord with the highest value, are givenbelow:

Adhesion to Carcass Stock Cord Treatment with Force to Strip Single End(grams) Compositions A-D S B R Natural Rubber The results conclusivelyshow that the adhesion is greater in A than D, that is, using theadhesive composition comprising triallyl cyanurate with only a traceamount of ringbound chlorine, as compared with the RFL dip alone. Whenthe ringbound chlorine content is high, as in B and C, the adhesion issubstantially greater, both with natural as well as styrene-butadienerubber.

Although polyester fibers are used in the example described in detailhereinabove, the invention is equally applicable to other fibrousmaterials useful for the reinforcement of rubber products, such ascotton, nylon, rayon and the like. The invention is particularly usefulin the field of automobile tires, where polyester cord is often usedalone or in conjunction with glass fibers as in the so-calledbelted-bias construction of tires.

As already pointed out above, the nature of the rubber which is bound tothe fibrous material, is not critical and may be either natural or asynthetic rubber. The application of the rubber to the reinforcingfibrous material is carried out by conventional known methods. Therubber stock applied may contain additives such as for instancevulcanizers, fillers, antioxidants and pigments.

What is claimed is:

l. A composition comprising an aqueous dispersion of A. 50-95parts of aresorcinol-formaldehyde-latex adhesive composition,

B. 5-50 parts of an aqueous dispersion of the reaction product of l. acomposition derived by reacting a triallyl cyanurate composition having0.058 to 3.0 ringbound chlorine, with 6-l0moles of resorcinol per moleof cyanurate; and 2. 0.2 to 0.6 mole of formaldehyde per mole ofresorcinol in (l). 2. The composition according to claim 1 wherein theringbound chlorine content is provided by at least one compound offormula:

wherein Y and Z are individually a chlorine, allyloxy or hydroxy group.

3. The composition according to claim 1 wherein the ringbound chlorinecontent in B is about 1.0 percent.

4. The composition according to claim 1 wherein the latex in theresorcinol-formaldehyde-latex adhesive composition is a mixture of apolyvinylpyridine-styrenbutadiene terpolymer latex and astyrene-butadiene copolymer latex.

UNITED STATES PATENT OFFICE CERTIFICATE OF COREC'EICN Patent No. 3, l h5 Dated February 7 Inventor s) RAYMOND BROI SMAN It is certified thaterror'appears in the above-identified patent and that said LettersPatent are hereby corrected as shown below:

Column 1, line 22, delete "625,1 8?" and substitute 652,1;87

Column 1, line 27, delete "la-tex" and substitute latex Column 1, line70, delete "3.05" and substitute 3.0 Column 2, line 14., delete "3.08"and substitute 3.0%

Column 2, line 6L after the word "percent" add the following For thepurpose of obtaining TAC with between 0.05 and Column 2, line 7L delete"ll C." and substitute Column 3, line 5, after the word "reaction" addthe following and then adjust with NaOH at the end of the reactionColumn 3, line 7, after the word "chlorine" insert 0 Column 3, line 50,after the word "film" insert Column Lt, line 38, after the number "50"insert Column L line 62, delete "(5)" and substitute (7 Column 5, line61, delete i 50F." and substitute 7 i 5 Column 5, line 63, delete "0.1,land 2.2 percent ringbound" and substitute 0,01%, 1% and 2.2% ring-boundColumn 6, line 11, after the word "ring-bound" insert the word chlorineColumn 8, line 1 delete "0.058 to 3.0" and substitute. 0.5% to 3.0%

Signed and sealed this 25th day of July 1972.

(SEAL) Attest:

EDWARD MJLETCHERJR ROBERT GOTTSCHALK. Attesting Officer Commissioner ofPatents

1. A COMPOSITION DERIVED BY REACTING A TRIALLYL CYANURATE COMPOSITIONHAVING 0.05 TO 3.0 PERCENT RING-BOUND COMPOSITION HAVING 0.05 TO 3.0PERCENT RING-BOUND CHLORINE, WITH 6-10 MOLES OR RESORCINOL PER MOLE OFCYANURATE; AND
 2. 0.2 TO 0.6 MOLE OF FORMALDEHYDE PER MOLE OF RESORINOLIN (1) THESE COMPOSITIONS ARE USEFUL IN BONDING RUBBER TO REINFORCINGFIBERS.
 2. 0.2 to 0.6 mole of formaldehyde per mole of resorcinol in(1).
 2. The composition according to claim 1 wherein the ringboundchlorine content is provided by at least one compound of formula:wherein Y and Z are individually a chlorine, allyloxy or hydroxy group.3. The composition according to claim 1 wherein the ringbound chlorinecontent in B is about 1.0 percent.
 4. The composition according to claim1 wherein the latex in the resorcinol-formaldehyde-latex adhesivecomposition is a mixture of a polyvinylpyridine-styrenbutadieneterpolymer latex and a styrene-butadiene copolymer latex.